CN104973591A - High-quality graphene and preparation method thereof - Google Patents
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Abstract
The invention relates to high-quality graphene and a preparation method thereof. The preparation method includes the steps of (1) wrap-embedding graphene oxide into the lamellas in expanded graphite to obtain a graphene oxide/expanded graphite mixture; and (2) performing thermal-treatment to the graphene oxide/expanded graphite mixture so that the expanded graphite can be stripped with assistance of a reaction force from high-temperature expansion reduction of the graphene oxide, thereby preparing the graphene powder. In the invention, the graphene oxide is wrap-embedded into the lamellas in the expanded graphite, and the expanded graphite is stripped-away with the impact force of a violent reaction in the high-temperature expansion reduction of the graphene oxide, thereby obtaining loosen graphene powder. The expanded graphene is controllable in the number of layers, is free of defect, is less in impurities and is high in purity.
Description
Technical field
The present invention relates to field of graphene, be specially high-quality graphene prepared by a kind of graphene oxide up-stripping expanded graphite with and preparation method thereof and application in conductive and heat-conductive film.
Background technology
Since Graphene was found from 2004, cause the great interest of scientific research circle immediately, become a large focus material of scientific research in recent years.Graphene is the bi-dimensional cellular shape structure formed by monolayer carbon atom close-packed arrays, its special physicochemical property: high-specific surface area, excellent electrical and thermal conductivity performance, good physical strength, make it have a wide range of applications in nanoelectronics, ultracapacitor, battery and sensor field.
The preparation of Graphene is the hot issue that people pay close attention to always, is directly connected to the subsequent applications of material.At present, prepare in a large number the method for Graphene maximum be based on Hummers method oxidation reduction process, first graphite is oxidized, obtains graphite oxide, then it is peeled off, eventually pass reduction treatment and obtain Graphene.But the Graphene that the method obtains also exists more defect, still there is larger gap with high-quality Graphene in property indices.And utilize expanded graphite the material of the strong oxidizing properties such as halogenide mostly will be utilized to process for Graphene prepared by raw material at present, inevitably bring impurity, affect the performance of Graphene; And it is lower to utilize the method such as microwave or hydro-thermal process expanded graphite to prepare the productive rate of Graphene, is unfavorable for extensive preparation.Therefore need exploitation a kind of can in a large number, low cost and the eco-friendly method preparing Graphene.
Utilize graphene dispersing solution to prepare the graphene film with better electrical and thermal conductivity and can be widely used in the field such as energy storage device and heat sink material.The preparation of current graphene film often adopts graphene oxide dispersion to be raw material, utilizes vacuum filtration process to prepare graphene oxide film, then obtains graphene film by chemistry or thermal reduction.Thermal reduction will be carried out in inertia or reducing atmosphere, and reduction temperature, up to 1000 DEG C, is unfavorable for preparation that is energy-saving and cost-reducing and flexible conductive film; Hydrazine hydrate cost is high, contaminate environment, and film is easily broken, cannot obtain the graphene film of high conductivity.
Summary of the invention
In the face of prior art Problems existing, a kind of method of high-quality zero defect Graphene, the Graphene prepared by the method and this Graphene can prepared in large quantities, is at low cost the object of the present invention is to provide to prepare the application in graphene film.
At this, on the one hand, the invention provides a kind of preparation method of high-quality graphene, comprising: graphene oxide parcel is embedded Expandable graphite sheet interlayer and obtains graphene oxide/expanded graphite mixture; And expanded graphite described in the reversed stress up-stripping of the graphene oxide of gained/expanded graphite mixture being heat-treated when utilizing described graphene oxide high-temperature expansion to reduce, thus obtained graphene powder.
The present invention utilizes expanded graphite and graphene oxide to be raw material, without the need to strong acid or other strong oxidizer as intercalator; Graphene oxide parcel is embedded the sheet interlayer of expanded graphite, when utilizing graphite oxide high-temperature expansion to reduce, expanded graphite lamella is peeled away by the surging force of vigorous reaction, obtains fluffy graphene powder, after expanding, the gained Graphene number of plies is controlled, zero defect, impurity is few, and purity is high.And gained Graphene productive rate is high, in water and in other organic solvents, high, the good dispersity of stability, is applicable to the preparation being applied to graphene film.Preparation method's technique of the present invention is simple, easy handling, with low cost, controllability is high, and whole reaction environmental pollution is little, without waste liquid generation, can in large quantities, at low cost, environmentally friendly prepare high-quality zero defect Graphene.
Preferably, described graphene oxide/expanded graphite mixture is prepared as follows: added by expanded graphite in graphene oxide water solution, be fully uniformly mixed, and obtains the mixed solution of expanded graphite graphene oxide; And gained mixed solution is dry, i.e. obtained described graphene oxide/expanded graphite mixture.In the present invention, by by graphene oxide and expanded graphite in a solvent mix and blend graphene oxide can be made to wrap up the sheet interlayer embedding expanded graphite.
Preferably, the massfraction of described graphene oxide water solution is 0.05 ~ 10mg/ml, is preferably 0.5 ~ 5mg/ml.
Preferably, the mass ratio of expanded graphite and graphene oxide is 10:1 ~ 1:50, is preferably 2:1 ~ 1:10.
Preferably, churning time is 30 minutes ~ 10 hours.
Preferably, described heat treated treatment temp is 100 ~ 1000 DEG C, is preferably 300 ~ 800 DEG C; Treatment time is 0.5 ~ 120 minute, is preferably 2 ~ 10 minutes.
Preferably, described preparation method also comprises: gained graphene powder is carried out in dispersion agent ultrasonic lift-off processing to form graphene dispersing solution; And by dry for the graphene dispersing solution of gained with the graphene powder of obtained high loft.
By carrying out ultrasonic stripping, the Graphene that the number of plies is less can be obtained.
Preferably, described dispersion agent is at least one in water, ethanol, methyl alcohol, Virahol, acetone, acetonitrile and DMF.
Preferably, the treatment time of described ultrasonic lift-off processing is 1 minute ~ 5 hours, is preferably 1 hour.
Preferably, the drying of graphene dispersing solution is spraying dry or lyophilize.
On the other hand, the invention provides the graphene powder prepared by above-mentioned preparation method, the number of plies of the graphene film after thermal expansion in gained graphite composite powder is at 20 ~ 30 layers, and lateral dimension is more than 30 μm; Carbon-to-oxygen ratio in described graphite composite powder is more than 20.The number of plies of the graphene film after ultrasonic drying in described graphite composite powder is 5 ~ 10 layers, and lateral dimension is more than 20 μm; Carbon-to-oxygen ratio in described graphite composite powder is more than 20.
Again on the one hand, the invention provides any one graphene powder above-mentioned and prepare the application in graphene film, comprise: described graphene powder is dispersed in dispersion agent and forms graphene suspension, film is formed by the mode of filtering coating, peel off from filter paper after drying, roll rear graphitization processing, obtained graphene film.
Preferably, the described dispersion agent in described application is at least one in water, ethanol, methyl alcohol, Virahol, acetone, acetonitrile and DMF.The concentration of described graphene suspension can regulate according to the thickness of graphene film to be prepared.
Preferably, the mode of described filtering coating is vacuum filtration or pressure filtration.
In the present invention, obtained graphene film thickness can reach 1 ~ 1000 μm.It has excellent heat-conductivity conducting performance, and its specific conductivity can reach 10 ~ 1000S/cm, and thermal conductivity can reach 100 ~ 1000W/ (mK), also has good snappiness, can not expand or breakage.
In the present invention, without the need to adding other surfactant in graphene suspension, obtained graphene film has good snappiness, can not expand or breakage, have excellent electrical and thermal conductivity performance.Heat conduction and heat radiation, ultracapacitor, solar cell, electromagnetic shielding can be widely used in and inhale the fields such as ripple.
Graphene of the present invention and method for manufacturing thin film thereof, simple to operate, with low cost, environmental friendliness, is applicable to industrialization scale operation.
Accompanying drawing explanation
Fig. 1 is the schema that graphene oxide up-stripping expanded graphite prepares high-quality graphene;
Fig. 2 is the present invention's vermiform expanded graphite SEM photo used;
Fig. 3 is the SEM photo after the expanded graphite thermal treatment not adding graphene oxide in comparative example;
Fig. 4 is the Graphene SEM photo that in embodiment 2 prepared by graphene oxide up-stripping expanded graphite;
Fig. 5 is the SEM photo of embodiment 2 supersound process postlyophilization gained Graphene;
Fig. 6 is obtained graphene film photo in embodiment 5.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The preparation method of high-quality graphene of the present invention, utilizes graphene oxide as subsidiary, and parcel embeds Expandable graphite sheet interlayer, and reversed stress up-stripping expanded graphite when utilizing graphite oxide high-temperature expansion to reduce is to prepare Graphene.Meanwhile, can also and solvent in ultrasonic stripping combine preparation high-quality Graphene.
Fig. 1 illustrates that the graphene oxide up-stripping expanded graphite of an embodiment of preparation in accordance with the present invention prepares the schema of high-quality graphene.This embodiment is illustrated below in conjunction with Fig. 1.
In present embodiment, the graphene oxide as raw material can be standby by Hummers legal system.Such as, but should be understood that in the present invention, do not limit the source of graphene oxide, it also directly can be bought or is prepared by other method.Expanded graphite as raw material is such as vermiform, and its SEM photo can see Fig. 2.
Then, expanded graphite is fully combined with graphene oxide, with the sheet interlayer making graphene oxide embed expanded graphite.As an example, can be that expanded graphite is joined in graphene oxide solution, stir and allow expanded graphite fully be combined with graphite oxide, make graphene oxide be embedded in the space of expanded graphite; Then drying is carried out.Wherein the massfraction of graphene oxide solution can be 0.05 ~ 10mg/ml, is preferably 0.5 ~ 5mg/ml.The mass ratio of expanded graphite and graphene oxide can be 10:1 ~ 1:50, is preferably 2:1 ~ 1:10.Churning time can be 30 minutes ~ 10 hours.Carry out dry temperature and can be 0 ~ 80 DEG C.
Then, the mixture of well-bound expanded graphite and graphene oxide is carried out vacuum high-temperature reduction (thermal treatment), and when utilizing graphite oxide high-temperature expansion to reduce, expanded graphite lamella is peeled away by the surging force of vigorous reaction, obtains fluffy graphene powder.Wherein, heat treated treatment temp can be 100 ~ 1000 DEG C, is preferably 300 ~ 800 DEG C.The heat treated treatment time can be 0.5 ~ 120 minute, is preferably 2 ~ 10 minutes.
By the graphene powder that aforesaid method is obtained, wherein the number of plies of graphene film can 20 ~ 30, and lateral dimension can more than 30 μm.Again, carbon-to-oxygen ratio wherein can more than 20.The SEM photo of this graphene powder is for example, see Fig. 4.
Further, graphene powder high-temperature expansion can also being peeled off gained carries out supersound process in dispersion agent, fully peels off, makes graphene dispersion form graphene dispersing solution in dispersion; And by dry for the graphene dispersing solution of gained with the graphene powder of obtained high loft.Wherein, the dispersion agent adopted includes but not limited at least one in water, ethanol, methyl alcohol, Virahol, acetone, acetonitrile and DMF.The time of ultrasonic lift-off processing can be 1 minute ~ 5 hours, is preferably 1 hour.The drying mode adopted such as can be spraying dry or lyophilize.
Can be 5 ~ 10 layers by the number of plies of the graphene film in the graphene powder that obtains after above-mentioned ultrasonic lift-off processing, lateral dimension can more than 20 μm.Again, carbon-to-oxygen ratio wherein can more than 20.The SEM photo of this graphene powder is for example, see Fig. 5.
The present invention utilizes expanded graphite and graphene oxide to be raw material, without the need to strong acid or other strong oxidizer as intercalator; Graphene oxide parcel is embedded the sheet interlayer of expanded graphite, when utilizing graphite oxide high-temperature expansion to reduce, expanded graphite lamella is peeled away by the surging force of vigorous reaction, obtains fluffy graphene powder, after expanding, the gained Graphene number of plies is controlled, zero defect, impurity is few, and purity is high.Meanwhile, can also combine to prepare higher-quality graphene powder with ultrasonic stripping in solvent.Described preparation method's technique is simple, easy handling, with low cost, controllability is high, and whole reaction environmental pollution is little, without waste liquid generation, can in large quantities, at low cost, environmentally friendly prepare high-quality zero defect Graphene.
And gained Graphene productive rate is high, in water and in other organic solvents, high, the good dispersity of stability, is applicable to the preparation being applied to graphene film.
Preparation gained Graphene being applied to graphene film can comprise the following steps: be dispersed in dispersion agent by graphene powder and form graphene suspension, film is formed by the mode of filtering coating, peel off from filter paper after drying, roll rear graphitization processing, obtained graphene film.Wherein, the dispersion agent adopted includes but not limited at least one in water, ethanol, methyl alcohol, Virahol, acetone, acetonitrile and DMF.The concentration of graphene suspension can regulate according to the thickness of graphene film to be prepared.That is, can by the thickness regulating the concentration of graphene suspension to regulate graphene film.Filter type comprises vacuum filtration or pressure filtration.
In aforesaid method, graphene film can be obtained without the need to adding other surfactant.The graphene film thickness obtained by aforesaid method can reach 1 ~ 1000 μm, and specific conductivity can reach 10 ~ 1000S/cm, and thermal conductivity can reach 100 ~ 1000W/ (mK).Fig. 6 illustrates the photo of the graphene film of an example.As shown in Figure 6, this graphene film has good snappiness, can not expand or breakage.Obtained graphene film has good snappiness, can not expand or breakage, have excellent electrical and thermal conductivity performance.Heat conduction and heat radiation, ultracapacitor, solar cell, electromagnetic shielding can be widely used in and inhale the fields such as ripple.
Beneficial effect of the present invention:
The present invention utilizes expanded graphite and graphene oxide to be raw material, and without the need to strong acid or other strong oxidizer as intercalator, after expanding, the gained Graphene number of plies is controlled, and impurity is few, and purity is high.The method technique is simple, easy handling, with low cost, controllability is high, and whole reaction environmental pollution is little, produces without waste liquid.Gained graphene dispersing solution is without the need to adding other surfactants, and obtained graphene film has good snappiness, can not expand or breakage, have excellent electrical and thermal conductivity performance.Graphene of the present invention and method for manufacturing thin film thereof, simple to operate, with low cost, environmental friendliness, is applicable to industrialization scale operation.
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiment; should understand; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The temperature that following example is concrete, time etc. are also only examples in OK range, and namely, those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Comparative example
Test as a comparison, under the high temperature of 600 DEG C, process 10min by after the expanded graphite drying not adding graphene oxide.Found that, compared with former expanded graphite (Fig. 2), expanded graphite can not be peeled away (Fig. 3) after pyroprocessing, still present vermiform, after supersound process, lamella is thicker, and solution dispersion is poor.
As can be seen here, in order to the stripping of expanded graphite successfully can be realized, prepare graphene powder, must other supplementary meanss be passed through.
Embodiment 1
Consult Fig. 1, Fig. 1 shows preparation method's process flow sheet that the embodiment of the present invention prepares Graphene, comprises the steps.
The first step, prepares graphite oxide: in the present embodiment, Graphite Powder 99 mean particle size is 325 orders.Hummers method is utilized to synthesize graphene oxide (GO).By 2g Graphite Powder 99,1g NaNO
3mix with the 230ml vitriol oil in ice-water bath, slowly add 6g KMnO
4.Then be warming up at 35 DEG C, after stirring 30min, add 92mL deionized water, be warming up to 98 DEG C of reaction 15min.Afterwards, add the dilution of 280mL water wherein, and use 5mL30%H
2o
2neutralize unnecessary KMnO
4.The color of mixing solutions is brown color, filtered while hot, with deionized water repetitive scrubbing to neutral, ultrasonicly obtains GO.
Second step, graphite oxide is to the embedded parcel of expanded graphite: 1g expanded graphite being joined 200ml massfraction is in the graphene oxide solution of 5mg/ml, stirring 5h allows expanded graphite fully be combined with graphene oxide, and graphene oxide is embedded in the space of expanded graphite.Then be block by mixture drying at 80 DEG C.
3rd step, graphene oxide up-stripping expanded graphite prepares Graphene: above-mentioned dried product exhibited is processed 10min under the high temperature of 600 DEG C, when utilizing graphite oxide high-temperature expansion to reduce, expanded graphite lamella is peeled away by the surging force of vigorous reaction, obtains fluffy graphene powder.
4th step, supersound process: 1g gained graphene powder is dispersed in supersound process 2h in the aqueous solution of 200ml, makes it fully peel off, forms graphene solution.The graphene powder of high loft is obtained after lyophilize.
In sum, in the method high-temperature expansion gained graphene powder, the number of plies of graphene film is below 30 layers, and lateral dimension is more than 30 μm.The Graphene number of plies after ultrasonic stripping is at 5 ~ 10 layers, and lateral dimension is more than 20 μm.Carbon-to-oxygen ratio is more than 20.
As can be seen here, the present invention successfully can realize the stripping of expanded graphite, realizes the heavy industrialization preparation of Graphene.
Embodiment 2
The step of preparation process of Graphene is as follows.
The first step, prepares graphite oxide: in the present embodiment, Graphite Powder 99 mean particle size is 800 orders.Hummers method is utilized to synthesize GO.As embodiment 1.
Second step, graphite oxide is to the embedded parcel of expanded graphite: 1g expanded graphite being joined 150ml massfraction is in the graphene oxide solution of 8mg/ml, stirring 5h allows expanded graphite fully be combined with graphene oxide, and graphene oxide is embedded in the space of expanded graphite.Then be block by mixture drying at 80 DEG C.
3rd step, graphene oxide up-stripping expanded graphite prepares Graphene: above-mentioned dried product exhibited is processed 10min under the high temperature of 800 DEG C, obtains fluffy graphene powder.Its SEM photo is see Fig. 4.
4th step, supersound process: 1g gained graphene powder is dispersed in supersound process 1.5h in the aqueous solution of 200ml, makes it fully peel off, forms graphene solution.The graphene powder of high loft is obtained after lyophilize.Its SEM photo is see Fig. 5.
In sum, in the method high-temperature expansion gained graphene powder, the number of plies of graphene film is below 30 layers, and lateral dimension is more than 20 μm.The Graphene number of plies after ultrasonic stripping is at 5 ~ 10 layers, and lateral dimension is more than 10 μm.Carbon-to-oxygen ratio is more than 20.
Embodiment 3
The step of preparation process of Graphene is as follows.
The first step, prepares graphite oxide: in the present embodiment, Graphite Powder 99 mean particle size is 3000 orders.Hummers method is utilized to synthesize GO.As embodiment 1.
Second step, graphite oxide is to the embedded parcel of expanded graphite: 1g expanded graphite being joined 150ml massfraction is in the graphene oxide solution of 8mg/ml, stirring 5h allows expanded graphite fully be combined with graphene oxide, and graphene oxide is embedded in the space of expanded graphite.Then be block by mixture drying at 80 DEG C.
3rd step, graphene oxide up-stripping expanded graphite prepares Graphene: above-mentioned dried product exhibited is processed 8min under the high temperature of 800 DEG C, obtains fluffy graphene powder.
4th step, supersound process: 1g gained graphene powder is dispersed in supersound process 1h in the aqueous solution of 200ml, makes it fully peel off, forms graphene solution.The graphene powder of high loft is obtained after lyophilize.
In sum, in the method high-temperature expansion gained graphene powder, the number of plies of graphene film is below 20 layers, and lateral dimension is more than 5 μm.The Graphene number of plies after ultrasonic stripping is at about 5 layers, and lateral dimension is more than 3 μm.Carbon-to-oxygen ratio is more than 20.
The embodiment of the present invention provides above-mentioned Graphene in order to prepare the method for graphene film further.Exemplify embodiment below to describe in detail.
Embodiment 4
Get the above-mentioned graphene powder of 50mg, be dissolved in the 400ml aqueous solution, supersound process 1h, obtains graphene dispersing solution.The nuclepore membrane filter of this graphene suspension diameter 5cm is carried out vacuum filtration, after filtration, filter cake is dried as in 40 ~ 80 DEG C of baking ovens.Make it peel off from filter paper after rolling, graphitization processing obtains graphene film.
Obtained by this example, graphene film thickness can reach 10 μm, and specific conductivity can reach 500S/cm, and thermal conductivity can reach 400W/ (mK).Illustrate that the graphene film that this example obtains has good electrical and thermal conductivity performance.
This example gained graphene film can be widely used in heat conduction and heat radiation, ultracapacitor, solar cell, electromagnetic shielding and inhale the fields such as ripple.
Embodiment 5
Get the above-mentioned graphene powder of 50mg, be dissolved in 400ml ethanolic soln, supersound process 1h, obtains graphene dispersing solution.The nuclepore membrane filter of this graphene suspension diameter 5cm is carried out vacuum filtration, after filtration, filter cake is dried as in 40 ~ 80 DEG C of baking ovens.Film directly can be peeled off from filter paper after drying, roll rear graphitization processing and obtain graphene film.
Obtained by this example, graphene film thickness can reach 5 μm, and specific conductivity can reach 800S/cm, and thermal conductivity can reach 500W/ (mK).Illustrate that the graphene film that this example obtains has good electrical and thermal conductivity performance.
This example gained graphene film can be widely used in heat conduction and heat radiation, ultracapacitor, solar cell, electromagnetic shielding and inhale the fields such as ripple.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. a preparation method for high-quality graphene, is characterized in that, comprising: graphene oxide parcel is embedded Expandable graphite sheet interlayer and obtains graphene oxide/expanded graphite mixture; And expanded graphite described in the reversed stress up-stripping of the graphene oxide of gained/expanded graphite mixture being heat-treated when utilizing described graphene oxide high-temperature expansion to reduce, thus obtained graphene powder.
2. preparation method according to claim 1, it is characterized in that, described graphene oxide/expanded graphite mixture is prepared as follows: added by expanded graphite in graphene oxide water solution, be fully uniformly mixed, and obtains the mixed solution of expanded graphite graphene oxide; And gained mixed solution is dry, i.e. obtained described graphene oxide/expanded graphite mixture.
3. preparation method according to claim 2, is characterized in that, the massfraction of described graphene oxide water solution is 0.05 ~ 10mg/ml, is preferably 0.5 ~ 5mg/ml.
4. the preparation method according to Claims 2 or 3, is characterized in that, the mass ratio of expanded graphite and graphene oxide is 10:1 ~ 1:50, is preferably 2:1 ~ 1:10.
5. preparation method according to any one of claim 1 to 4, is characterized in that, described heat treated treatment temp is 100 ~ 1000 DEG C, is preferably 300 ~ 800 DEG C; Treatment time is 0.5 ~ 120 minute, is preferably 2 ~ 10 minutes.
6. preparation method according to any one of claim 1 to 5, is characterized in that, also comprises: gained graphene powder is carried out in dispersion agent ultrasonic lift-off processing to form graphene dispersing solution; And by dry for the graphene dispersing solution of gained with the graphene powder of obtained high loft.
7. preparation method according to claim 6, is characterized in that, described dispersion agent is at least one in water, ethanol, methyl alcohol, Virahol, acetone, acetonitrile and DMF; The treatment time of described ultrasonic lift-off processing is 1 minute ~ 5 hours.
8. the preparation method according to claim 6 or 7, is characterized in that, described drying is spraying dry or lyophilize.
9. a graphene powder prepared by the preparation method according to any one of claim 1 to 5, is characterized in that, the number of plies of the graphene film in described graphite composite powder is at 20 ~ 30 layers, and lateral dimension is more than 30 μm; Carbon-to-oxygen ratio in described graphite composite powder is more than 20.
10. a graphene powder prepared by the preparation method according to any one of claim 6 to 8, is characterized in that, the number of plies of the graphene film in described graphite composite powder is 5 ~ 10 layers, and lateral dimension is more than 20 μm; Carbon-to-oxygen ratio in described graphite composite powder is more than 20.
Graphene powder described in 11. 1 kinds of claims 9 or 10 is preparing the application in graphene film, it is characterized in that, comprise: described graphene powder is dispersed in dispersion agent and forms graphene suspension, film is formed by the mode of filtering coating, peel off from filter paper after drying, roll rear graphitization processing, obtained graphene film.
12. application according to claim 11, is characterized in that, the mode of described filtering coating is vacuum filtration or pressure filtration.
13. application according to claim 12, is characterized in that, the thickness of described graphene film is 1 ~ 1000 μm.
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| CN105949884A (en) * | 2016-06-07 | 2016-09-21 | 江南大学 | Preparation method of liquid phase stripping high-concentration graphene ink |
| CN106672951A (en) * | 2016-12-14 | 2017-05-17 | 北京化工大学 | Environment-friendly, high-efficiency and large-scale graphene preparation method |
| CN109665518A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of preparation method of highly conductive graphene |
| CN110577215A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | high-dispersion graphene oxide powder and preparation method and application thereof |
| CN109755027A (en) * | 2019-01-10 | 2019-05-14 | 中国科学院金属研究所 | Composite graphite alkene film, high-energy ultracapacitor and intelligent flexible device |
| CN109755027B (en) * | 2019-01-10 | 2021-01-19 | 中国科学院金属研究所 | Composite graphene film, high-energy supercapacitor and intelligent flexible device |
| CN110127682B (en) * | 2019-05-28 | 2021-07-23 | 郑州新世纪材料基因组工程研究院有限公司 | Graphene heat exchange membrane and preparation method thereof, graphene heat exchange coating and preparation method thereof, and composite material |
| CN110127682A (en) * | 2019-05-28 | 2019-08-16 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of graphene heat exchange film and preparation method thereof, graphene heat exchange coating and preparation method thereof, composite material |
| CN110482537A (en) * | 2019-09-10 | 2019-11-22 | 北京中石伟业科技无锡有限公司 | A kind of dispersing agent and its application that can moderately reduce graphene oxide slurry viscosity |
| CN112812534A (en) * | 2020-12-31 | 2021-05-18 | 广东墨睿科技有限公司 | Preparation method of heat-conducting graphene PC composite material |
| CN114408908A (en) * | 2021-12-31 | 2022-04-29 | 厦门凯纳石墨烯技术股份有限公司 | Graphene heat dissipation film and preparation method thereof |
| CN114715888A (en) * | 2022-03-29 | 2022-07-08 | 临海伟星新型建材有限公司 | High-thermal-conductivity graphite composite film and preparation method thereof |
| CN114715888B (en) * | 2022-03-29 | 2023-09-05 | 临海伟星新型建材有限公司 | High-heat-conductivity graphite composite film and preparation method thereof |
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